Ammoniated agricultural material



May 9, 1944. v Q M|LLAR v Re. 22,477

AMMONIATED AGRICULTURAL MATERIAL AS LIVESTOCK FEED AND PROCESS OF PRODUCING SAME Original Filed Aug. 28, 1940 I10 g a R a; 95 n: ILI 0. ILL

0 6o 90 420 \so I2 AMMONIA paessuneuusume) THE TEMPERATURE OBTAIN- ED av sue-Teams AIR DRY SUGAR BEET PULP o cam-Am 8 Z5 Q. 2 0 U RELATION BETWEEN AM- E momnmm TEMPERATURE 0 AND THE NITROGEN CONTENT 0 OFTHE AMMoMATEu SUGAR E Bccr PULP- 24 5o I30 240 250 TEMPERATURE "a the present invention silage during the ammoniation Reissued May 9, 1944 momma acnrcuurnnar. MATERIAL AS LIVESTOCK rnnn AND raocnss F PRODUCING SAME Harvey O. Millar, Western Springs,- Ill.,' assignor to The Quaker Oats. Company, corporation. of, New Jersey 2,293,845, dated August 25, 194;, se-

Original No.

Chicago, 111., a

rial'No. 354,5'l3fiAfugust 28,=-1940.- Application for reissue 19,;1il43, Serial No. 495,299

15 Claims. (01. 99- -2) The present invention relates toa new and improved livestock feed derived from agricultural materials, and it relates more particularly to 'a protein food for ruminants and to a proces of producing the same.

In the western part of the United States, where the amount of rainfall'is small and where feeds are consequently very valuable, sugar-beet pulp and silages, such as corn silage and sunflower silage, constitute important livestock feeds. However, both sugar-beet pulp and silage are undesirably low in protein, and a simple, economical method or increasing their nitrogen so as to be available to ruminants asprotein is highly desirable.

The object of the present invention is toobviate the foregoing disadvantages of sugar-beetpirlp and silage as a food for ruminants.

A further object is to provide an iniproved live-, stock feed which is rich in nitrogen'in a form that may be converted by ruminants into avail-r able protein.

Another object is economical method of converting sugar -beet pulp and silages into livestock food which can be utilized by ruminants as a source of protein.

It is further contemplated in accordancewith to incorporate,- simple; non-proteinaceous nitrogen compounds in beet pulp and silage in such a formthat, ruminants may utilize the same as nitrogenous-components of their diet. v

I have found that the foregoing objects may be attained in accordance with the present-invention, one aspect of which includes the preparation of an improved livestock food from sugarbeet pulp or silage, by ammoniating either or both of these agricultural materials, thereby imthe provision of a simple and increases the total nitrogen content of the raw material-for example, from 4 to 'l per cent. The nitrogen thus imparted is practically all in a. water-soluble form, this being contrary to the results obtained when peat, starch, and dextrose are ammoniated. There is every indication to believe that the nitrogen contained in the ammoniated product is present in a form that constitutes a satisfactory source of protein nitrogen for ruminants. The nitrogen thus imparted is believed to be in a non-protein form, but apparently certain microorganisms in the ruminants stomach are capable of converting these simple non-proteinaceous nitrogen compounds to a protein or proteins which are then rendered available to the animal.

: In order more clearly to disclose the nature of the present invention, certain embodiments thereof will-now-be described. It should be un-, derstood, however, that this is done solely for illustrative. purposes and is not to be construed as a limitation upon thescope of the appended claimsrr parting to the treated material a substantial amount or water-soluble, non-protein nitrogen in a form which isconvertible by ruminants into available prote The ammoniation may be carried out by treating the beet pulp or silage with anhydrous ammonia gas under superatmospheric pressure and temperature conditions. for example, at a pressure ranging from 5 to 1200 pounds gauge, at a temperature varying from room temperature to 250' C4, and tor a period varying from a Iew minutes to several hours. Preferably, the ammoniatlon is carried out at a pressure of from 10 to 200 pounds gauge, at a temperature of from 40 to 125' 0., and for a period varying from 15 minutes to 3 hours.

The nitrogen imparted to the beet pulp or step substantially The invention will be described with reference to the accompanyingflgures' of the drawing, wherein; a A v Figure 1 is a graphical representation showing generally the relation between the resulting temperaturesof-air-dry sugar-beet pulp when the;same is subjected to' varying ammonia pressings; and

Eig2 is a graphical representation showing generally the relation, between the ammoniation temperatures and" the nitrogen'contents of ammoniated sugar-beet pulp -Th'e ammoniation of beet pulp or silage is preferably accomplished in accordance with the present invention by placing the raw material in a .cylinder, autoclave, or bomb, depending upon the particular pressure and temperature conditions desired during the ammoniation step. The ammoniation cylinder may be steam-jacketed or otherwise heated, depending upon the particular temperature at which the reaction is to be carried out. Th ammoniation vessel is preferably provided with suitable means so that the vessel may be rotated or the contents thereof agitated during the ammoniationperiod.

As a matter of convenience, the ammoniation o1 beet pulp will first be described, and thereafter the ammoniation of silage will be disclosed.

The ammoniation of beet pulp.-The ammoniation of beet pulp may be carried out by placing the original sugar-beet pulp, with or without the addition of moisture, into the abovedescribed ammoniation vessel and then treating the contents with anhydrous gaseous ammonia under superatmospheric conditions. The moisture content oi thevoriginal pulp has been found to exert no significant influence upon the amount or total or water-insoluble nitrogen fixed dur- The temperature obtained by subjecting as the ammoniation chamber revolved and the ammonia was fixed.

The results indicate that a considerable amountci heat is liberated during the ammoniation or sugar-beet pulp, with the temperature increasing as the pressure is raised.

Tarn II Marbeet pulp to certain ammonia pressures and the nitrogen content or the ammoniated pulp 1 [Nitrogen values on moistureiree belie] Dried beet pulp Ammonhted product Watersa gzpls Momma Maximum 3 m Pm fig: Time insoluble eel-ma Moisture irm'utlle moniated obtained added nitrogen cent Per cent Per cent Pin cent us 1.7a can: an s. as r 2. on can an see me ans: as e 1.1: as. aw 4.11 am 11.00 m ts l-t as: w i 1.5 1H M g 0.106 sec 1.70 85.14 t

an um- 10 min. I

ing the ammoniation step. This may be seen from an inspection of Table I, which gives the total water-insoluble nitrogen content of, various ammon'lated samples prepared from pulp of various moisture contents. The untreated original pulp had a moisture content of 8.1 per cent and a total nitrogen content of 1.8 per cent, oi which 1.46 per cent was water-insoluble.

Teen: ,1

Influence of the moisture content of dried sugarbeet pulp on the amount and character of the nitrogen fixed by ammoniation I [Nitrogen values on moisture-tree basis] 7 Ammoniated product Moisture content Tun arglmow e a ammonipressure Total itf 3 m 6::

nod nitmgen nitrogen item the added nitrogen Lbs. per Percent Home 0min. Percent Percent Percent Percent 8. 1 l 1 2o 4. so 1. so 86. 92 8. 4 15. 0 1 60 4. 11 2. 09 77. B9 7. 6 21. 4 1 4. l5 1. 85 92. 9. 0 52. 4 1 00 3. N 1. '16 87. 29 6. 8

l Premire was allowed to drop during the hour.

The data indicate that the moisture content of the pulphad no influence upon the nitrogen fixed during ammoniation. The last column of Table I, headed Moisture, percent," indicates the moisture content of the ammoniated product after it was air-dried.

The ammcniation or sugar-beet pulp (or one hour at diiierent ammonia pressures, without the addition 'of external heat, is shown in Table II. The ammonia pressures, except for sample 8, were maintained during the entire periods at the values shown in the table. In sample 8,

however, the pressure was allowed to decrease l The relations of Table 11 between pressure and maximum temperature obtained by the reaction mass are shown in Fig. l. The'net amount of nitrogen fixed increased as the pressure and tem perature increased. But, as shown in TableII, there is little change. in the amount of waterinsoluble nitrogen imparted to the pu l!- Thus,

for example, sample 8, ammcniated for only 10 minutes, contained 3.89 per cent nitrogen.

Materials treated as shownin Table II will,

- when removed from the reaction chamber, re-

tain a certain, amount of tree ammonia which may be removed it desiredby any suitable means, such as by subjecting the material to a high vacuum, thus recovering the ammonia. Preterably a suitable reactant, such as monocalcium phosphate, may be added to the material, which will fix the ammonia. result in a feed or improved mineral content as well as improved nitrogenous value.

The influence of, temperature and pressure on the nitrogen content of ammoniated sugar-beet pulp is indicated by the results shown in Table III and Fig. 2. During this study, samples were ammoniated in a cylinder, autoclave, or bomb, according to the temperature and pressure desired. The heat of the reaction mass was augmented by putting steam through theiacket oi the autoclave or by placing the bomb in a sand The data oi! Table III show that the amount of total nitrogen imparted to the pulp was very closely relatedto the ammoniation temperature, and furthermore that the water-soluble nitrogen derived from the added nitrogen was above -84 per cent, except when very high temperatures a period of 25 minutes as for a longer period.

were employed, as in sample '7. The data indicate that at corresponding temperatures equally good results are obtained by ammoniatlng tor Ammoniation at a pressure above 1,000 pounds per square inch for 2 hours at 232-O.-gavea product containing 10.72 per cent nitrogen (see Such a procedure will sample .7), most oi which was water-insoluble. Under similar conditions, except that the temperature was lower, a. product having a total nitrogen content of 1.61 per cent was obtained (see sample 8).

TABLE III Influence of ammontation temperature and pressure on the nitrogen content of ammoniated sugar-beet pulp [Nitrogen values on moisture-free basis] Dried beet pulp Ammonlated product Sample No. Moisture Watep y content 'lemper- Total Pressure Time insoluble deriv from Moisture Color when am ature nitrogen mounted nitrogen the added nitrogen Hours Per cent Per cm: Per cent Per cent 1.60 1.46 8.1 Grey. 8.1 1 3. 53 1. 73 86.01 8.9 Olive green. 8. 1 1 4. 16 1. 73 89.46 8. 7 Brown. 8. 1 l 4. 62 1. 94 84. 8. 5 D0. 8.1 1 5.25 1.59 96.44 7.5 Do. 15. 0 3 6. B0 2. 26 84.1]! 11. 4 Dark brown. 15. 0 3 7.09 2. 10 88. 16 9. 5 Do. 8. 1 2 10. 72 6. 34 46. 49 7. 0 Black. 8. 1 2 7. 61 l. 01 100.00 7. 0 Dark brown. 15.0 1 4. 60 1. 69 92. 33 8.4 Light brown.

8. l 0. 41 4. 58 1. 71 91. 61 8. 5 Brown.

tested by feeding them to dairy cows and sheep. I

Sample 1 was the original untreated pulp. Sample 2 was a composite of ammoniated sample and was predominantly green, with a nitrogen content of about 4.4 per cent. Sample 3 was also a composite of ammoniated samples and was dark brown, with a nitrogen content of sugar-beet pulp containing 4.4 per cent nitrogen were readily eaten by year-old dairy stock.

.Ammoniation of com silage-Com silage was obtained in the spring of the year from the lower portion of a cement silo. The first and second portions of the silage secured for this work contained per cent and 6'1 per cent moisture, respectively. Part of the sample containing 50 per cent moisture was allowed to air-dry to 1'7 .5 per cent moisture, while another portion was allowed to dry to 9 per cent.

The various samples of silage were then ammoniated under conditions shown in Table IV. The first eight samples were ammoniated in a cylinder with no heat applied, whereas the last two were ammoniated in a bomb heated in a sand bath. The quantity of silage used completely filled the ammoniation vessel in each case.

\ TABLE IV The ammoniation of cured corn silage [Nitrogen values on moisture-lree basis) Ammoniated product Melange A Maxim um can u mmonia temper- Sample when amadded Pressure ature Tom Watermoniated obtained mm insoluble Moisture I nitrogen Hours Per cent Per cent Per cent Original (dry) 1 g} 1 The results indicate that the original silage contained only 1.26 per cent total and 0.61 per cent water-insoluble nitrogen. The nitrogen about 6.3 per cent. The results of 'the palatabllity tests showed that, when fed alone to dairy cattle, samples 1 and 2 appeared to be equally content oi the samples ammoniated at all four moisture values increased with the amount oi ammonia used. Moreover, the samples which were permitted to dry before ammoniation attained a lower temperature and flxed 'les ammonia than those which were not permitted to dry.

The samples containing 6'! per cent moisture received a measured amount oi ammonia. One

ounce added to a 10-pound sample gave a product having 2.34 per centnitrogen. This exhibited only faint odors of ammonia when taken from the chamber. when the amount of ammonia was increased to 12 ounces, the nitrogen content of the product increased only very slightly, but the product emitted a strong ammonia odor. The nitrogen added to the samples ammoniated at low temperature and pressure was practically all in a water-soluble form, whereas high-temperature and high-pressure ammoniation gave a.

black product having 7.8 per cent total and 4.69 per cent water-insoluble nitrogen.

(a) Palatabilitv of ammoniated corn silage.- Ihe ammoniated' samples oi" cornsilage, except samples 9 and 10, prep red from air-dried samples were readily eaten by year-old dairy stock. Thenitrogen content or the product compares favorably to that of the best hays.

From the foregoing detailed description it will be apparent that many variations may be made without departing from the spirit and scope or the invention. Thus, for example, time, temperature, and pressure relationships obtaining during the ammoniation treatment may be varied within very wide limits. Other forms of equipment than those 'hereinbeiore mentioned may be 4. A method oi preparing an improved livestock feed from an agricultural roughage selected from the group consisting of sugar-beet pulp, corn silage and sunflower silage, which includes the step .or treating said .roughage with anhydrous ammonia gas under superatmospheric pressure and temperature conditions to impart substituted where desired. Many other variations will be apparent to thosejskllled in .the art. I therefore intend to be limited only in accords ance with the following patent claims.

I claim: 1 v

1. A method of preparing an improved livestock food from an agricultural roughage which includes the step of ammoniating said roughage I to impart thereto a substantial amount 01 nitrogenous material utilizable for nutritional purposes.

2. A method of preparing an improved livestock feed from an agricultural roughage which includes the step of treating said roughage with anhydrous ammonia gas under superatmospheric pressure and temperature conditions to impart thereto a substantial amount of nitrogeneous the step of ammoniating said roughage to impart thereto a substantial amount of nitrogeneous material utilizable for nutritional purposes.

corn silage, and sunflower silage, which includes thereto a substantial amount of nitrogeneous material utilizable for nutritional p poses.

5. The method of claim 2 wherein said treatment with ammonia gas is carried out at a pressure within the range of 5 to 1200 pounds gauge,"

at a temperature within the range of room temperature to 250 C., and for a period or time within the range of 15 minutes to 3 hours.

6. The method 01' claim 4 wherein said treatment with ammonia gas is carried out at a pressure within the range of 5 to 1200 pounds gauge, at a temperature within the range 01' room temperature to 250 (3., and for a period or time within the range of 15 minutes to 3 hours.

' '7. The method of claim 2 wherein said treatment with ammonia gas is carried out at a pressure within the range or 10 to 200 pounds gauge, at a temperature within the range of 40 to C., and for a; period 0! from 15 minutes to 3 hours. r

8. The method of claim 4 wherein said treatment with ammonia gas is carried out at a pressure within the range oi 10 to 200 poimds gauge.

I at a temperature within the range of 40 to 125 C.,'and for a period of from 15 minutes to 3 hours. a Y I 9. An improved livestock feed for ruminants comprising a member 01 the group consisting of ammoniated sugar-beet pulp and ammoniated corn silage.

10. An improved livestock feed for ruminants comprising ammoniated sugar-beet pulp- 11. An improved livestock feed derived by ammoniation of an agricultural roughage selected from the group consisting of sugar-beet pulp, corn silage, and sunflower silage, and characterized by a nitrogen content'substantially greater than that of the unammoniated material, said nitrogen being'in a form utilizable for nutritional pu p s- 1,2. A method of improving the color oi. a livestock iced prepared from sugar-beet pulp that comprises treating said pulp with ammonia.-

13. A method of improving the color oi, a livestock feed prepared from sugar-beet pulp that comprises treating sugar-beet pulp in accordance with the method of claim 2. r

14. An improved livestock feed comprising ammoniated agricultural roughage.

15. An improved livestock feed comprising ammoniated agricultural materials containing nonproteinaceous nitrogen compounds usableby ruminants as a source of protein.

' HARVEY C. MILLAR. 

